This invention relates to electrochromic devices and more particularly electrochromic mirrors which are useful as light controllable elements such as light controllable windows (smart windows) for buildings, automobiles and passenger vehicles and various types of light controllable glasses for indoor decoration or partitions; display devices; antidazzle mirrors for automobiles; and decoration mirrors for indoor use.
A conventional electrochromic device such as a conventional type of antidazzle mirror as disclosed in Japanese Patent Laid-Open Publication No. 63-18336 is known which mirror comprises a chromogenic material in the form of a film obtained by sputtering or vacuum-depositing an inorganic oxide such as tungsten oxide (WO3) over a transparent electrically conductive film.
Such an electrochromic antidazzle mirror is manufacture by a film forming operation carried out under vacuum conditions, resulting in increased production cost. A demand has therefore been placed on an electrochromic mirror which can be manufactured with inexpensive materials and by a simple and easy method.
A method has also been proposed in which to use a viologen compound as a component constituting an electrochromic device. However, further improvements on this method are demanded because the purification of viologen requires time and effort and the life or duration of coloration or decoloration functions of the device may be shortened, resulting from impurities such as an acid even in small amounts mixed into the system of the device.
It is an object of the present invention to solve the aforementioned problems by using specific electrically conductive high molecular compounds as a color developing film or layer.
According to the present invention, there is provided an electrochromic device comprising two conductive substrates, at least one of which is transparent, an ion conductive layer disposed therebetween and an electrochromic color developing layer disposed between the ion conductive layer and at least either one of the two conductive substrates and containing (A) a compound having a viologen structure represented by the formula 
wherein Xxe2x88x92 and Yxe2x88x92 may be the same or different and each are a counter anion selected from the group consisting of a halogen anion, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CH3COOxe2x88x92 and CH3(C6H4)SO3xe2x88x92 and (B) 4,4xe2x80x2-dipyridyl and/or a mono-substituted 4,4xe2x80x2-dipyridinium salt represented by the formula 
wherein Xxe2x88x92 is a counter anion selected from the group consisting of a halogen anion, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CH3COOxe2x88x92 and CH3(C6H4)SO3xe2x88x92.
According, to another aspect of the present invention, there is provided an electrochromic device all of which components are solid.
According to further another embodiment of the present invention, there is provided an electrochromic mirror which comprises a reflective conductive substrate, a transparent substrate, an ion conductive layer disposed therebetween and an electrochromic color developing layer disposed between the ion conductive and the reflective conductive substrate or transparent substrate.
The two conductive substrates, at least one of which is transparent, are used in the present invention. These substrates may be any type of substrates as long as they function as an electrode. More specifically, each of the conductive substrate may be those entirely formed from an electrically conductive material or those comprised of a non-electrically conductive substrate and an electrode layer disposed thereon. An electrochromic mirror according to the present invention includes a pair of such electrically conductive substrates, at least one of which is transparent and the other of which is reflective of light or non-reflective opaque. These transparent, reflective and opaque substrates may have a flat or curved surface and may be deformable under stress.
The transparent conductive substrate may generally exemplified by a laminate comprising a transparent substrate and a transparent electrode layer formed thereon. The reflective electrically conductive substrate may be exemplified by (1) a laminate comprising a transparent or opaque substrate and a reflective electrode layer formed thereon, (2) a laminate comprising a substrate having a transparent electrode layer on one of its surfaces and a reflective electrode layer on the other surface, (3) a laminate comprising a transparent substrate having a reflective layer formed thereon and further a transparent electrode layer formed thereon and (4) a plate-like substrate which itself functions as a reflective layer and an electrode. The non-reflective opaque conductive substrate is exemplified by a substrate selected from various metal plates or a laminate comprising a non-conductive opaque substrate such as various opaque plastics, ceramics, glasses and woods and an electrode formed on its surface.
No particular limitations is imposed on the transparent substrate. It may thus be a color or colorless glass, a reinforced glass and a resin of color or colorless transparency. Specific examples of such a resin include polyethylene terephthalate, polyamide, polysulfone, polyether sulfone, polyether etherketone, polyphenylene sulfide, polycarbonate, polyimide, polymethyl methacrylate and polystyrene.
The term xe2x80x9ctransparencyxe2x80x9d used herein designates an optical transmission which is in the range from 10 to 100 percent. The substrates used for the invention have a smooth surface at normal temperature.
There is no particular restriction to the transparent electrode layer as long as it meets the requirements for achieving the purpose of the present invention. Specific examples of the electrode layer include electrically conductive films such as thin films of various types of metals such as gold, silver, chrome, copper and tungsten or of metal oxides such as ITO (In2O3xe2x80x94SnO2), tin oxide, silver oxide, zinc oxide and vanadium oxide.
The electrode has a film thickness in the range of usually 100 to 5,000 and preferably 500 to 3,000 angstrom. The surface resistance of the electrode is usually in the range of 0.5-500 and preferably 1-50 xcexa9/sq.
No particular limitation is imposed on a method of forming the electrode layer. Any suitable conventional methods may be employed, depending upon the kind of metal and metal oxide constituting the electrode. In general, the formation of the electrode layer is carried out by vacuum evaporation, ion plating, sputtering and a sol-gel method. The thickness of the electrode layer is selected within the range such that the transparency thereof is not affected. The electrode layer may be partially provided with an opaque electrode-activator for the purpose of imparting oxidation-reduction capability, electric conductivity and electric double layer capacitance, the electrode-activator being provided in an amount such that the transparency of the entire electrode layer is not harmed. Electrode activators eligible for the purpose of the invention arc metals such as copper, silver, gold, platinum, iron, tungsten, titanium and lithium, organic materials having oxidation-reduction capability such as polyaniline, polythiophen, polypyrrole and phthalocyanine, carbon materials such as active carbon and graphite and metal oxides such as V2O5, WO3, MnO2, NiO and Ir2O3 and mixtures thereof. A variety of resins may be used for integrating the electrode activator in the electrode. The opaque electrode activator may applied onto an electrode by forming on an ITO transparent electrode a composition comprising an active carbon fiber, graphite and an acrylic resin into a micro pattern in the shape of stripes or by forming on a thin-film of gold a composition comprising V2O5, acetylene black and butyl rubber in the shape of a mesh.
No particular limitation is imposed on the reflective electrode layer as long as it is electrochemically stable and has a specular surface. Eligible reflective electrode layers include metal films such as of gold, platinum, tungsten, tantalum, rhenium, osmium, iridium, silver, nickel and palladium and alloy films such as of platinum-palladium, platinum-rhodium and stainless steel. The reflective electrode layer is necessarily disposed onto a substrate or a transparent substrate with the reflectiveness and specularity of the layer maintained. The reflective electrode layer is formed onto a substrate by any suitable conventional method such as vacuum deposition, ion-plating and sputtering.
No particular limitation is imposed on a substrate on which the reflective electrode layer is disposed. The substrate may be transparent or opaque. Specific examples of the substrate include those as exemplified with respect to the transparent substrate described above, a variety of plastics, resins, glasses, woods and stones.
No particular limitation is imposed on a material for the above-mentioned reflective plate or layer as long as it can provide a specular surface. For example, silver, chrome, aluminum and stainless steel are eligible.
The plate-like substrate having a reflective layer and functioning as an electrode may be exemplified by the substrates exemplified with respect to the reflective electrode among which are self-supportive.
An ion conductive material used for the inventive electrochromic mirror is disposed so as to be sandwiched between a reflective electrically conductive substrate or non-reflective opaque substrate and a transparent electrically conductive substrate (these substrates are hereinafter referred to as counter-conductive substrates). No particular limitation is imposed on a method of disposing the ion conductive material between the counter-conductive substrates. A method may be employed in which the ion conductive material is injected into the space provided between the substrates which are placed, facing each other and then sealed at the edges of the opposed surfaces, by vacuum injection, atmospheric injection or a meniscus method. Alternatively, a method may be employed in which the layer of the ion conductive material is formed on the electrode layer of one of the electrically conductive substrates and then put together with the other electrically conductive substrate. Further alternatively, a method may be employed in which a film-like ion conductive material is inserted between a pair of glasses to form a laminated glass.
The term xe2x80x9cion conductive materialxe2x80x9d designates materials which can color, decolor and discolor an electrochromic material hereinafter described. The ion conductive material has preferably an ion conductivity of 1xc3x9710xe2x88x927S/cm or more at room temperature. No particular limitation is imposed on the ion conductive material, which may thus be liquid, gel or solid. Solid ion conductive materials are particularly preferred for the purpose of the invention so as to obtain an electrochromic mirror which is overall solid and excelled in various performances for practical usage.
Eligible liquid ion conductive materials are those dissolving a supporting electrolyte such as salts, acids and alkalis in a solvent.
Although any suitable solvents may be used as long as they can dissolve a supporting electrolyte, preferred are those having polarity. Specific example of such solvents are water and an organic polar solvent such as methanol, ethanol, propylene carbonate, ethylene carbonate, dimethylsulfoxide, dimethoxyethane, acetonitrile, r-butyrolactone, r-valerolactone, sulforan, dimethylformamide, dimethoxyethane, tetrahydrofuran, propionnitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, dimethylacetoamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, trimethylphosphate and polyethylene glycol. Preferred are propylene carbonate, ethylene carbonate, dimethylsulfoxide, dimethoxyethane, acetonitrile, xc3xa3-butyrolactone, sulforan, dioxolane, dimethylformamide, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetoamide, methylpyrrolidinone, dimethylsulfoxide, trimethylphosphate and polyethylene glycol. These may be used singlely or in combination.
Although not restricted, salts used as a supporting electrolyte may be alkali metal salts, inorganic ion salts such as alkaline earth metal salts, quaternary ammonium salts and cyclic quaternary ammonium salts. Specific examples of such salts include alkali metal salts of lithium, sodium or potassium such as LiClO4, LiSCN, LiBF4, LiAsF6, LiCF3SO3, LiPF6, LiI, NaI, NaSCN, NaClO4, NaBF4, NaAsF6, KSCN and KCl, quaternary ammonium salts or cyclic quaternary ammonium salts such as (CH3)4NBF4, (C2H5)4NBF4, (n-C4H9)4NBF4, (C2H5)4NBr, (C2H5)4NClO4 and (n-C4H9)4NClO4 and mixtures thereof.
Acids used as a supporting electrolyte may be exemplified by inorganic acids and organic acids, specific examples of which include sulfuric acid, hydrochloric acid, phosphoric acid, sulfonic acid carboxylic acid.
Alkalis used as a supporting electrolyte include sodium hydroxide, potassium hydroxide and lithium hydroxide.
The gelatinized-liquid ion conductive material may be those which are gelatinized or made to be viscous by adding a polymer or a gelatinizer to the above-mentioned liquid ion conductive material.
No particular limitation is imposed on the polymers, which thus may be polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, polyurethane, polyacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropyleneoxide and nafion.
Preferred examples of gelatinizers are oxyethylenemethacrylate, oxyethyleneacrylate, urethaneacrylate, acrylamide and agar-agar.
No particular limitation is imposed on the solid ion conductive material as long as it is solid at room temperature and ion conductive. Preferred examples of such solid ion conductive materials are polyethylencoxide, the polymer of oxyethylenemethacrylate, nafion, polystylene sulfonate, Li3N, Na-xcex2-Al2O3 and Sn(HPO4)2H2O. Particularly preferred are polymer solid electrolytes obtained by polymerizing a polyethylencoxide-based compound, an oxyalkyleneacrylate-based compound or a urethaneacrylate-based compound.
A first examples of such polymer solid electrolytes are those obtained by solidifying a composition (hereinafter referred to as Composition A) containing the above-described organic polar solvent and supporting electrolyte and a urethaneacrylate of the formula 
wherein R1 and R2 may be the same or different and are each a group of formula (4), (5) or (6) below, R3 and R4 may be the same or different and are each a C1-C20, preferably C2-C12 divalent hydrocarbon residue, Y is selected from a polyether unit, a polyester unit, a polycarbonate unit and the mixed unit thereof and n is an integer of 1-100, preferably 1-50 and more preferably 1-20.
Formulae (4), (5) and (6) are represented by 
wherein R5, R6 and R7 may be the same or different and are each a hydrogen atom or a C1-C3 alkyl group and R8 is a C1-C20, preferably C2-C8 organic residue of divalent through quatervalent.
Specific examples of such organic residues are a hydrocarbon residue such as alkyltolyl, alkyltetratolyl and alkylene of the formula 
wherein R9 is a C1-C3 alkyl group or hydrogen, p is an integer of 0-6 and if p is greater than 2 the groups of R9 may be the same or different.
The hydrocarbon residue may be a group part of which hydrogen atoms are substituted by an oxygen-containing hydrocarbon group such as a C1-C6, preferably C1-C3 alkoxy group and a C6-C12 aryloxy group.
Specific examples of group R8 in formulae (3) thorough (5) are those represented by the following formulae: 
Each of the divalent hydrocarbon residues represented by R3 and R4 in formula (3) is exemplified by a divalent chain-like hydrocarbon group, an aromatic hydrocarbon group and an alicyclic-containing hydrocarbon group. Specific examples of the chain-like divalent hydrocarbon group are those represented by formula (7) above.
Specific examples of the aromatic hydrocarbon group and alicyclic-containing hydrocarbon group are those represented by the following formulae 
wherein R10 and R11 may be the same or different and each are a phenylene group, a phenylene group having an alkyl substituent, a cycloalkylene group and a cycloalkylene group having an alkyl substituent, R12, R13, R14 and R15 may be the same or different and each are a hydrogen atom or a C1-C3 alkyl group and q is an integer from 1 to 5.
Specific examples of the groups R3 and R4 in formula (II) are those represented by the following formulae: 
In formula (II), Y indicates a polyether unit, a polyester unit, a polycarbonate unit and a mixed unit thereof. Each of these units is represented by the following formulae: 
In formulae (a) through (d), R16 through R21 may be the same or different and are each a C1-C20, preferably C2-C12 divalent hydrocarbon residue. R21 is particularly preferably a C2-C6 divalent hydrocarbon residue. R16 through R21 are preferably straight or branched alkylene groups among which methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and propylene groups are preferred for R18, and ethylene and propylene groups are preferred for R16, R17 and R19 through R21. The letter xe2x80x9cmxe2x80x9d in formula (a) is an integer of 2-300, preferably 10-200, the letter xe2x80x9crxe2x80x9d is an integer of 1-300, preferably 2-200, the letter xe2x80x9csxe2x80x9d is an integer of 1-200, preferably 2-100, the letter xe2x80x9ctxe2x80x9d is an integer of 1-200, preferably 2-100 and the letter xe2x80x9cuxe2x80x9d is an integer of 1-300, preferably 10-200.
Each unit represented by formulae (a) through (d) may be a copolymer of the same or different units. Namely, if there exist a plurality of groups of each R16 through R21, groups of each R16, R17, R18, R19, R20 and R21 may be the same or different. Preferred examples of such copolymers include copolymers of ethylene oxide and copolymers of propylene oxide.
An urethaneacrylate of formula (II) has a molecular weight in the range of 2,500-30,000, preferably 3,000-20,000.
The urethaneacrylate has preferably 2-6, more preferably 2-4 polymerization functional groups per molecule.
The urethaneacrylate may be prepared by any suitable conventional method.
An organic polar solvent (organic nonaqueous solvent) is added in an amount of 100-200, preferably 200-900 weight parts per 100 parts of the urethaneacrylate. Too less amount of the addition of the organic polar solvent would result in insufficient ion conductivity, while too much amount of the addition would cause reduced mechanical strength.
No particular limitation is imposed on a supporting electrolyte as long as it is not obstructive in achievement of the purpose of the invention. Preferred are those already exemplified above. The supporting electrolyte should be added in an amount of 0.1-30, preferably 1-20 weight percent of the organic polar solvent.
Composition (A) is obtained by solidifying the above-described essential components, namely, the above-described urethaneacrylate, organic nonaqueous solvent and supporting electrolyte. If necessary, any suitable optional components may be added to Composition (A) as long as they are not obstructive to the achievement of the purpose of the invention. Such components may be crosslinkers and photo- or thermal polymerization initiators.
The solid polymeric electrolyte of the first example may be inserted between a pair of electrically conductive substrates disposed, facing each other by injecting Composition (A) into a selected space between the substrates in a conventional manner and curing the same. The term xe2x80x9ccuringxe2x80x9d used herein designates a state where polymerizing or crosslinking component is brought to be cured with the progress of polymerization (polycondensation) or crosslinking and thus the composition does not flow at room temperature. The composition thus cured has the basic structure in the form of network.
A second example of the polymeric solid electrolyte is obtained by solidifying a composition (hereinafter referred to as Composition (B)) comprising an organic polar solvent, a supporting electrolyte, a monofunctional acryloyle-modified polyalkylene oxide of formula (18) below and a polyfunctional acryloyle-modified polyalkylene oxide of formula (19) or (20) below.
Formula (18) is represented by 
wherein R22, R23, R24 and R25 may be the same or different and are each hydrogen and an alkyl group having 1-5 carbon atoms and n is an integer of greater than 1.
Specific examples of the alkyl group include methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl and n-pentyl. Preferred for R22, R23 and R24 are hydrogen and a methyl group. Preferred for R25 are hydrogen, methyl and ethyl groups.
The letter xe2x80x9cnxe2x80x2xe2x80x9d in formula (18) is an integer of greater than 1, usually from 1 to 100, preferably from 2 to 50 and more preferably from 2 to 30.
Specific examples of the compound represented by formula (18) are those having 1-100, preferably 2-50 and more preferably 1-20 oxyalkylene units, such as methoxypolyethylene glycol methacrylate, methoxypolypropylene glycol methacrylate, ethoxypolyethylene glycol methacrylate, ethoxypolypropylene glycol methacrylate, methoxypolyethylene glycol acrylate, methoxypolypropylene glycol acrylate, ethoxypolyethylene glycol acrylate, ethoxypolypropylene glycol acrylate and mixtures thereof.
If n is greater than 2, the compound may be those having different oxyalkylene units, that is, copolymerized oxyalkylene units which for instance have 1-50, preferably 1-20 oxyethylene units and 1-50, preferably 1-20 oxypropylene units. Specific examples of such compounds are (ethylenexc2x7propylene) glycol methacrylate, ethoxypoly (ethylenexc2x7propylene) glycol methacrylate, methoxypoly (ethylenexc2x7propylene) glycol methacrylate, methoxypoly (ethylenexc2x7propylene) glycol acrylate, ethoxypoly methoxypoly (ethylenexc2x7propylene) glycol acrylate and mixtures thereof.
The polyfunctional acryloyl-modified polyalkylene oxide may be a bifunctional acryloyl-modified polyalkylene oxide represented by the formula 
wherein R26, R27, R28 and R29 are each hydrogen and a C1-C5 alkyl group and mxe2x80x2 is an integer of greater than 1; or a polyfunctional acryloyl-modified polyalkylene oxide having more than three functional groups represented by the formula 
wherein R30, R31 and R32 are each hydrogen and a C1-C5 alkyl group, pxe2x80x2 is an integer of greater than 1, qxe2x80x2 is an integer from 2 to 4 and L is a connecting group of valence indicated by qxe2x80x2.
In formula (19), R26, R27, R28 and R29 are each hydrogen or a C1-C5 alkyl group, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl, t-butyl and n-pentyl groups among which preferred are hydrogen and methyl. The letter xe2x80x9cmxe2x80x2xe2x80x9d in formula (19) is an integer of greater than 1, usually from 1 to 100, preferably from 2 to 50, and more preferably from 2 to 30. Preferred examples of compounds of formula (19) are those having 1-100, preferably 2-50, more preferably 1-20 oxyalkylene units such as polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate and mixtures thereof.
If m is greater than 2, the compound of formula (19) may be those having, different oxyalkylene units, that is, polymerized oxyalkylene unit having, 1-50, preferably 1-20 oxyethylene units and 1-50, preferably 1-20 oxypropylene units, such as poly(ethylenexc2x7propylene)glycol dimethacrylate, poly(ethylenexc2x7propylene)glycol diacrylate and mixtures thereof.
In formula (20), R30, R31 and R32 are each hydrogen or a C1-C5 alkyl group, such as methyl, ethyl, i-propyl, n-propyl, n-butyl, t-butyl and n-pentyl. Particularly preferred for R30, R31 and R32 are hydrogen and a methyl group.
The letter xe2x80x9cpxe2x80x9d is an integer of greater than 1, usually from 1 to 100, preferably from 2 to 50 and more preferably from 2 to 30.
The letter xe2x80x9cqxe2x80x9d indicates the number of connecting group xe2x80x9cLxe2x80x9d and is an integer from 2 to 4.
Connecting group xe2x80x9cLxe2x80x9d is a divalent, trivalent or quatravalent hydrocarbon group having 1-30, preferably 1-20 carbon atoms.
Such divalent hydrocarbon groups may be alkylene, arylene, arylalkylene, alkylarylene and hydrocarbon groups having those groups as the base skeleton. Specific examples of such hydrocarbon groups are those represented by the following formulae 
Such trivalent hydrocarbon groups may he alkyltryl, aryltryl, arylalkyltryl, alkylaryltryl and hydrocarbon groups having those groups as a base skeleton. Specific examples of such hydrocarbon groups are those represented by the following formulae 
Such quatravalent hydrocarbon groups may be alkyltetraryl, aryltetraryl, arylalkyltetraryl, alkylaryltetraryl and hydrocarbon groups having those groups as the base skelton. Specific examples of such hydrocarbon groups are those represented by the following formulae: 
Specific examples of the compounds of formula (20) are those having 1-100, preferably 1-50, more preferably 1-20 of an oxyalkylene units such as trimethylolpropanetri(polyethylene glycol acrylate), trimethylolpropanetri(polyethylene glycol methaacrylate), trimethylolpropanetri(polypropylene glycol acrylate), trimethylolpropanetri(polypropylene glycol methaacrylate), tetramethylolmethanetetra(polyethylene glycol acrylate), tetramethylolmethanetetra(polyethylene glycol methaacrylate) tetramethylolmethanetetra(polypropylene glycol acrylate), tetramethylolmethanetetra(polypropylene glycol methaacrylate), 2,2-bis[4-(acryloxypolyethoxy)phenyl]propane, 2,2-bis[4-(methaacryloxypolyethoxy)phenyl]propane, 2,2-bis[4-(acryloxypolyisopropoxy)phenyl]propane, 2,2-bis[4-(methaacryloxypolyisopropoxy)phenyl]propane and mixtures thereof.
If p is more than 2, the compounds of formula (20) may be those having different oxyalkylene units, that is, polymerized oxyalkylene units having 1-50, preferably 1-20 of oxyethylene units and 1-50, preferably 1-20 oxypropylene units. Specific examples of such compounds include trimethylolpropanetri(poly(ethylenexc2x7propylene)glycol acrylate), trimethylolpropanetri(poly(ethylenexc2x7propylene)glycol methaacrylate), tetramethylolmethanetetra(poly(ethylenexc2x7propylene)glycol acrylate), tetramethylolmethanetetra(poly(ethylenexc2x7propylene)glycol acrylate) and mixtures thereof.
Needless to mention, there may be used a combination of a difunctional acryloyl-modified polyalkyleneoxide of formula (19) and a polyfunctional acryloyl-modified polyalkyleneoxide of formula (20). When these compounds are used in combination, the weight ratio of a compound of formula (19) to that of formula (20) is in the range from 0.01/99.9 to 99.9/0.01, preferably from 1/99 to 99/1 and more preferably from 20/80 to 80/20. The weight ratio of a compound of formula (18) to a polyfunctional acryloyl-modified polyalkyleneoxide is in the range of usually from 1/0.001 to 1/1, preferably from 1/0.05 to 1/0.5.
The above-described organic polar solvent should be added in an amount of 50-800, preferably 100-500 weight percent based on the total weight of the compound of formula (18) and the polyfunctional acryloyl-modified polyalkyleneoxide.
The above-described supporting electrolyte should be added in an amount of 1-30, preferably 3-20 weight percent based on the total weight of the compound of formula (18), the polyfunctional acryloyl-modified polyalkyleneoxide and the organic polar solvent.
If necessary, another optional components other than the above-described components may be added to Composition (B) as long as they do not give adverse effect on the inventive electrochromic mirror. Although not restricted, such components may be photopolymerization initiators or thermal polymerization initiators. These initiators should be added in an amount of 0.005-5, preferably 0.01-3 weight percent based on the total weight of the compound of formula (18) and the polyfunctional acryloyl-modified polyalkylene oxide.
The polymeric solid electrolyte described above as a second example may be inserted between a pair of electrically conductive substrates facing each other by injecting Composition (B) into a selected site therebetween by any suitable method. The xe2x80x9ccuringxe2x80x9d used herein designates a state where a polymerizable or crosslinkable component such as monofunctional or polyfunctional acryloyl-modified polyalkyleneoxide is brought to be cured with the progress of polymerization or crosslinking and hence the composition entirely stays unfluidized. In this case, the monofunctional or polyfunctional acryloyl-modified polyalkyleneoxide has the basic structure in the form of networks.
Needless to mention, ion conductive materials other than those as described above are also eligible.
Next, an electrochromic color developing layer constituting the inventive electrochromic mirror is described. The electrochromic color developing layer used in the present invention is characterized in that it contains (A) a compound having a viologen structure represented by the formula (hereinafter referred to as Compound A) 
and (B) 4,4xe2x80x2-dipyridyl (hereinafter referred to as Compound B1) or a 1-substituted 4,4xe2x80x2-dipyridinium salt (hereinafter referred to as Compound B2) represented by the formula 
Compounds B1 and B2 are hereunder generically referred to as Compound B.
First, Compound (A) is described.
Compound (A) has a viologen structure represented by formula (1) above.
In formula (1), Xxe2x88x92 and Yxe2x88x92 are each a counter anion and may be the same or different and an anion selected from the group consisting of a halogen anion, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CH3COOxe2x88x92 and CH3(C6H4)S)3xe2x88x92. The halogen anion may be Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 and I31 .
No limitation is imposed on the compound having a viologen structure as long as it possesses electrochromic properties. Such a compound is exemplified by high molecular weight compounds and low molecular weight compounds. Such high molecular weight compounds may be those having a viologen structural unit or a unit containing a viologen structure as a repeating unit or those having at their terminal ends a viologen structural unit as well as those having molecular chains part of which is substituted with a group having a viologen structure. Such low molecular weight compounds may be those having a viologen structure. The high molecular weight compounds having repeating units may be those of which side or main chain is formed by viologen structural units. There is no restriction to the repeating units forming the main chains of high molecular weight compounds if the side chains are formed by viologen structural units. Such repeating units forming the main chain may be hydrocarbon units, oxygen-containing units, nitrogen-containing units, polysiloxane units and copolymerized units thereof.
The compound having a viologen structure may be a polymer or copolymer represented by the formula 
The letter xe2x80x9cmxe2x80x9d indicates an integer of more than 1, preferably from 1 to 1,000, and the letter xe2x80x9cnxe2x80x9d indicates an integer of more than 0, preferably from 0 to 1,000. R33 is a C1-C20, preferably C1-C12 divalent hydrocarbon residue or merely indicates the bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, namely covalently bond. Specific examples of hydrocarbon groups include aliphatic hydrocarbon groups such as methylene, ethylene, propylene, tetramethylene, pentamethylene and hexamethylene and aromatic hydrocarbon groups such as phenylene, biphenylene and benzylidene. Specific examples of oxygen-containing hydrocarbon groups include aliphatic alkoxylene groups such as xe2x80x94OCH2xe2x80x94, xe2x80x94OCH2CH2xe2x80x94 and xe2x80x94OCH2CH2CH2xe2x80x94, aliphatic dialkoxylene groups such as xe2x80x94OCH2CH2Oxe2x80x94 and xe2x80x94OCH2CH2CH2O xe2x80x94, aromatic aryloxy groups such as xe2x80x94O(C6H4)xe2x80x94 and xe2x80x94OCH2(C6H4)xe2x80x94 and aromatic diaryloxy groups such as xe2x80x94O(C6H4)O and xe2x80x94OCH2(C6H4)Oxe2x80x94.
Xxe2x88x92 and Yxe2x88x92 each indicate a counter anion which is a monovalent anion, with respect to viologen and may be the same or different. Xxe2x88x92 and Yxe2x88x92 may be a halogen anion such as Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 and Ixe2x88x92, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CH3COOxe2x88x92 and CH3(C6H4)SO3xe2x88x92.
R34, R35 and R36 are each a C1-C20, preferably C1-C12 hydrocarbon group and a hetero atom-containing substituent and a halogen atom. Preferred hydrocarbon groups for R34, R35 and R36 are alkyl groups such as methyl, ethyl, propyl and hexyl and an aryl group such as phenyl, tolyl, benzyl and naphtyl. Preferred hetero atom-containing substituents are a C1-C20, preferably C1-C12 oxygen-containing hydrocarbon group, amide, amino and cyano groups. Such oxygen-containing hydrocarbon groups include an alkoxyl group such as methoxy and ethoxy an aryloxy group such as phenoxy and triloxy, a carboxyl group and a residual carboxylic acid ester.
In the case where the compound of formula (21) is a copolymer, the copolymerization pattern of the repeating units may be that of block-, random- or alternate copolymerization.
The compound having a viologen structure may also be a polymer or copolymer represented by the formula 
In formula (22), m, n and Xxe2x88x92 and Yxe2x88x92 are the same as defined in formula (21) and n is preferably 0. R37 and R39 may be the same or different and are each the same as those as defined with respect to R33 in formula (21) and R38 and R40 may the same or different and each are the same as those as defined with respect to R34 in formula (21).
In the case where a compound of formula (22) is a copolymer, the copolymerization pattern of the repeating units may be that of block, random or alternate polymerization.
Moreover, the compound having a viologen structure may also be a polymer or copolymer represented by the formula 
In formula (23), m, n and Xxe2x88x92 and Yxe2x88x92 are the same as those as defined in formula (21) and n is preferably 0. R41 is the same as those as defined with respect to R33 in formula (21) and R42, R43 and R44 may be the same or different and each are the same as those as defined with respect to R34 in formula (21).
In the case where the compound of formula (23) is a copolymer, the copolymerization pattern of the repeating units may be that of block, random or alternate of polymerization.
Furthermore, the compound having a viologen structure may be a copolymer represented by the formula 
In formula (24), p is an integer of more than 0, preferably from 0 to 20, q is an integer of 0-1,000 and R45 is the same as those as defined with respect to R33 in formula (21).
Further alternatively, the compound having a viologen structure may also be a polymer or copolymer of the formula 
In formula (25), R is a C1-C10 alkyl group, r is an integer of more than 1, preferably from 1 to 1,000, R46 is the same as those as defined with respect to R33 in formula (21) and R47 is the same as those as defined with respect to R33 in formula (21).
Typical examples of the compound having a viologen structure used for the present invention have been exemplified by compounds of formulae (21) through (25). Specific examples of compounds which are included within the range of these formulae and which are not included within the range of these formulae but eligible for the invention are given below. Pr in the following formulae indicates a propyl group. 
Next, Compound B is described.
As described above, Compound B is encompassed by 4,4xe2x80x2-dipyridyl (Compound B1) and a 1-substituted 4,4xe2x80x2-dipyridinium salt (Compound B2) represented by formula (2).
The substitution structure of 1-substituted 4,4xe2x80x2-dipyridinium salt may be in the form of mixtures.
No particular limitation is imposed on Compound B2 as long as it possesses electrochromic properties when used in combination with Compound A. Compound B2 may thus be high molecular weight or low molecular weight compounds. Such high molecular weight compounds may be those having repeating units containing a 1-substituted-4,4xe2x80x2-dipyridinium salt or those having at their terminal ends a 1-substituted-4,4xe2x80x2-dipyridinium salt. Such low weight molecular weight compounds may be those having hydrogen or lower molecular weight substituent at the terminal end of a 1-substituted-4,4xe2x80x2-dipyridinium salt.
The high molecular weight compounds having repeating units may be those of which side or main chains arc formed of 1-substituted-4,4xe2x80x2-dipyridinium salts. There is no restriction to the repeating units forming the main chains of high molecular weight compounds if 1-substituted-4,4xe2x80x2-dipyridinium salts forms the side chains. Such repeating units may be hydrocarbon units, oxygen-containing units, nitrogen-containing units, polysiloxane units and copolymerized units thereof.
Compound B2 may be a polymer or copolymer represented by the formula 
The letter xe2x80x9cmxe2x80x9d indicates an integer of more than 1, preferably from 1 to 1,000, and the letter xe2x80x9cnxe2x80x9d indicates an integer of more than 0, preferably from 0 to 1,000. R48 is a C1-C20, preferably C1-C12 divalent hydrocarbon, residue or merely indicates the bond of the viologen group directly to a polymer chain not through the hydrocarbon residue, namely covalently bond. Specific examples of hydrocarbon groups include aliphatic hydrocarbon groups such as methylene, ethylene, propylene, tetramethylene, pentamethylene and hexamethylene and aromatic hydrocarbon groups such as phenylene, biphenylene and benzylidene. Specific examples of oxygen-containing hydrocarbon groups include aliphatic alkoxylene groups such as xe2x80x94OCH2xe2x80x94, xe2x80x94OCH2CH2xe2x80x94 and xe2x80x94OCH2CH2CH2xe2x80x94, aliphatic dialkoxylene groups such as xe2x80x94OCH2CH2Oxe2x80x94 and xe2x80x94OCH2CH2CH2Oxe2x80x94, aromatic aryloxy groups such as xe2x80x94O(C6H4)xe2x80x94 and xe2x80x94OCH2(C6H4)xe2x80x94 and aromatic diaryloxy groups such as xe2x80x94O(C6H4)O and xe2x80x94OCH2(C6H4)Oxe2x80x94.
Xxe2x88x92 indicates a counter anion which is a monovalent anion, with respect to viologen and may be same or different. Xxe2x88x92 may be a halogen anion such as Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 and Ixe2x88x92, ClO4xe2x88x92, BF4xe2x88x92, PF6xe2x88x92, CH3COOxe2x88x92 and CH3(C6H4)SO3xe2x88x92.
R49 and R50 are each a C1-C20, preferably C1-C12 hydrocarbon group and a hetero atom-containing substituent and a halogen atom. Preferred hydrocarbon groups for R49 and R50 are alkyl groups such as methyl, ethyl, propyl and hexyl and an aryl group such as phenyl, tolyl, benzyl and naphtyl. Preferred hetero atom-containing substituents are a C1-C20, preferably C1-C12 oxygen-containing hydrocarbon group, amide, amino and cyano groups. Such oxygen-containing hydrocarbon groups include an alkoxyl group such as methoxy and ethoxy an aryloxy group such as phenoxy and triloxy, a carboxyl group and a residual carboxylic acid ester.
In the case where the compound of formula (26) is a copolymer, the copolymerization pattern of the repeating units may be that of block-, random- or alternate copolymerization.
Alternatively, Compound B2 may be a polymer or copolymer represented by the formula 
In formula (27), m, n and Xxe2x88x92 are the same as defined in formula (26) and n is preferably 0). R51 is the same as defined with respect to R48 in formula (48). R52 and R53 may be the same or different and are each the same as those as defined with respect to R49 in formula (26).
In formula (27) R51 is allowed to be bonded to any position of the pyridine ring to which R53 bonds but may be bonded to the pyridine ring free of substituents.
In the case where a compound of formula (27) is a copolymer, the copolymerization pattern of the repeating units may be that of block-, random- or alternate copolymerization.
Furthermore, Compound B2 may be a polymer or copolymer represented by the formula 
In formula (28), R is a C1-C10 alkyl group, r is an integer of greater than 1, preferably from 1 to 1,000. R54 is the same as those defined with respect to R48 in formula (26).
Typical examples of eligible compounds having the above-described 1-substituted dipyridine structure for the present invention have been described in reference with formula (26) through (28). Specific examples of compounds encompassed by these formulae and compounds not encompassed thereby but eligible for the invention are as follows: 
Compounds A, B1 and B2 can be produced by any suitable known method.
As described above, the electrochromic layer of the present invention contains Compound A and Compound B and is typically formed from a composition comprising Compound A and Compound B. Such a composition may be produced by a method in which Compounds A and B are produced separately from each other and then mixed together. Alternatively, the composition may be produced by reacting precursors or materials inducing Compounds A and B, respectively under desired conditions. From an industrial point of view, the latter method is preferred. For example, Compound B1 is a commercial product and thus easily available. Therefore, Compound B1 used as a starting material is reacted with a polymerizing or non-polymerizing halogenated compound of more than equimolecular amounts, usually 1-3 times greater mole of Compound B1 (4,4xe2x80x2-dipyridyl) in an inactive solvent i.e. an organic solvent which is not reactive with 4,4xe2x80x2-dipyridyl and free of halogen, such as alcohols, pentane, hexane, cyclohexane, diethylether, acctone, benzene, toluene, ethyl acetate, acetonitrile, dimethyl formamide and dimethyl sulfoxide, and then heated with stirring for a certain period of time, followed by vacuum-distillation of the solvent and the unreacted halogenated compound so as to obtain a mixture of Compound A, Compound B2 and Compound B1 remaining unreacted.
Although recrystallization or column separation is generally employed for the purification of viologen, such an operation may be omitted and it is sufficient only to remove the halogenated compound used as a starting material and solvent used for reaction.
The molar composition ratio of Compound A to Compound B is within the range of 1:99-99.9:0.1, preferably 80:20-99.9:0.1, and more preferably 95:5-99:1.
The electrochromic layer of the present invention contains essentially Compound A and Compound B but is almost entirely composed of only Compound A and Compound B. The electrochromic layer is obtained by forming these compounds into a film or layer, over the above-mentioned conductive substrate. No particular limitation is imposed on a method of forming the film or layer. A method is employed in which to apply and dry a solution obtained by dissolving Compounds A and B in a solvent. Alternatively, a method is employed in which Compounds A and B are cast over the above-mentioned conductive substrate and then cooled after being melted by heating. The former method is particularly preferred.
No particular limitation is imposed on a solvent used in the former method as long as it is volatile. Examples of such solvents are dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, N-methyl pyrrolidone, xcex3-valerolactone, dimethoxyethane, acetnitrile, propionenitrile, tetrahydrofuran, dioxane, methanol, ethanol, propanol, chloroform, toluene, benzene, nitrobenzene and dioxolan.
The applying method may be cast coating, spin coating, dip coating, spray coating, blade coating and flow coating. Drying may also be conducted by any conventional method.
The electrochromic color developing layer is easily oxidized or reduced by being applied with a voltage and thus colored or discolored.
The electrochromic color developing layer is generally 0.01 to 50 xcexcm, preferably 0.1-20 xcexcm.
If necessary, another compounds promoting color developing may be used in combination with Compounds A and B.